CN103875096B - Nonaqueous secondary battery - Google Patents
Nonaqueous secondary battery Download PDFInfo
- Publication number
- CN103875096B CN103875096B CN201180074108.XA CN201180074108A CN103875096B CN 103875096 B CN103875096 B CN 103875096B CN 201180074108 A CN201180074108 A CN 201180074108A CN 103875096 B CN103875096 B CN 103875096B
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- active material
- negative electrode
- electrode active
- material layer
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Abstract
In a nonaqueous secondary battery (100A) which comprises a negative electrode sheet (240A) wherein a negative electrode active material layer (243A) is held by a negative electrode collector (241A), it is preferable that a binder (730) contained in the negative electrode active material layer (243A) contains a rubber-based binder or a resin that has a binder function. In this case, it is preferable that the rubber-based binder or the resin that has a binder function is contained at a higher density in a portion (A1) near the surface of the negative electrode active material layer (243A) in the negative electrode active material layer (243A).
Description
Technical field
The present invention relates to non-aqueous secondary battery.
In this manual, " secondary cell " generally refers to rechargeable batteries, (typical including lithium secondary battery
Lithium rechargeable battery), the so-called accumulator such as Ni-MH battery.In addition, " active substance " is to refer in this manual
The chemical seed that reversibly occlusion becomes charge carrier with releasing (typically insertion and deintercalation) in the secondary battery (for example, exists
In lithium rechargeable battery be lithium ion) material.In addition, " non-aqueous secondary battery " refers to that nonaqueous electrolyte is (for example, non-aqueous
Electrolyte) as electrolyte secondary cell.
Background technology
For example, for lithium rechargeable battery, disclosed in Japanese Unexamined Patent Publication 2008-84742 publication (JP2008-84742A)
It is provided with the araneose film of Kynoar (PVDF) on the surface of electrode composition layer.According to this publication, using this
The araneose film of PVDF, the generation of suppression electrode block, inside battery will not be mixed into, the few raising of fraction defective can be obtained
The lithium rechargeable battery of reliability.
That is, the disclosure according to this publication, when electrode composition layer surface does not form the film of PVDF, is fitting in electrode composition
The bonding plane adhesive electrodes powder of the adhesive tape of layer surface.But, when electrode composition layer surface is formed with the film of PVDF, fitting in
The adhesive tape of electrode composition layer surface will not adhesive electrodes.Therefore, this publication discloses electrode to be difficult to come off, inhibit electrode
The generation of chip.
Prior art literature
Patent documentation
Patent documentation 1：JP2008-84742A
Content of the invention
However, in the non-aqueous secondary battery with lithium rechargeable battery as representative, using negative electrode active material will be contained
The negative electrode active material layer of plasmid is held in the negative pole of negative electrode collector.Lithium rechargeable battery particularly is being used as to make vehicle
Power supply (the vehicle traction battery) of the electromotor of driving wheel when it is desirable to suitable at a high speed under electric discharge.In addition, make use of system
It is desirable to charging under at a high speed in the charging of the regeneration of energy when dynamic.In electric discharge at high speeds, negative electrode active material layer requires
Moment releases substantial amounts of lithium ion.In charging at high speeds, negative electrode active material layer requires being capable of the substantial amounts of lithium of moment occlusion
Ion.
In addition, vehicle traction battery is due to being placed on outdoor, according to weather, the season of the region using vehicle, be really
Protect required function the wide temperature environment of the low temperature from 60 DEG C about of high temperature to -30 DEG C about.As described above, vehicle drives
When employing battery and repeating discharge and recharge at high speeds, correspondingly repeat putting of considerable amount of lithium ion in negative electrode active material layer
Go out and occlusion.But, particularly at low ambient temperatures, the releasing of the lithium ion in this negative electrode active material layer, the reaction of occlusion
Speed reduces, and becomes the factor of the response speed limiting battery.
The non-aqueous secondary battery of one embodiment of the present invention possesses negative electrode collector and is maintained at negative electrode collector
Negative electrode active material layer.Therefore, negative electrode active material layer comprises negative electrode active material particle and binding agent.Binding agent comprises rubber
It is binding agent or the resin with binding agent function.Elastomeric adhesive or there is the resin of binding agent function be mostly included in
The near surface of the negative electrode active material layer in negative electrode active material layer.
According to above-mentioned non-aqueous secondary battery, the near surface in negative electrode active material layer contains rubber series bonding in a large number
Agent or the resin with binding agent function.Using above-mentioned elastomeric adhesive or the resin with binding agent function, can be higher
Maintain negative electrode active material layer release, occlusion become the chemical seed of charge carrier in the secondary battery (for example, in lithium ion
In secondary cell be lithium ion) when response speed.Thus, particularly under -15 DEG C about of low temperature environment, can be by charge and discharge
Resistance increment rate after electricity circulation suppresses relatively low.
Now, when near surface is the region in negative electrode active material layer from a surface to 1/4 thickness, by negative electrode active material
Elastomeric adhesive contained by the near surface of matter layer and the resin with binding agent function carry out total mass concentration A and incite somebody to action
The partly contained elastomeric adhesive except near surface of negative electrode active material layer enters with the resin with binding agent function
The ratio A/B of total mass concentration B of row is about 2.0≤(A/B)≤3.8.
Other elastomeric adhesive contained by binding agent or the resin with binding agent function can be to be scattered in water
The binding agent of property solvent.In addition, elastomeric adhesive is, for example, SBR.In addition, the resin with binding agent function includes acrylic acid
It is binding agent or imide series binding agent.Here, acrylic adhesive is for example, in poly(ethylene oxide), polyethylene
At least one binding agent.
In addition, the 150 of negative electrode active material particle tap densities can be 1g/cm3More than.Thus, it is possible to improve negative
The peel strength of pole active material layer.
In addition, this non-aqueous secondary battery is preferably constituted in the form of lithium ion battery.In addition, non-aqueous secondary battery can
So that multiple battery combination to be constituted.Even if further, since above-mentioned non-aqueous secondary battery and set of cells are at -15 DEG C about
Also resistance increment rate can be suppressed relatively low under temperature environment, be particularly suitable as the purposes of vehicle traction battery.
Brief description
Fig. 1 is the figure of an example of the structure representing lithium rechargeable battery.
Fig. 2 is the figure of the rolled electrode bodies representing lithium rechargeable battery.
Fig. 3 is the sectional view representing the III-III section in Fig. 2.
Fig. 4 is the sectional view of the structure representing positive electrode active material layer.
Fig. 5 is the sectional view of the structure representing negative electrode active material layer.
Fig. 6 is the side view with the welding position of electrode terminal for the uncoated portion representing rolled electrode bodies.
Fig. 7 is the figure of the state during charging schematically showing lithium rechargeable battery.
Fig. 8 is the figure of the state during electric discharge schematically showing lithium rechargeable battery.
Fig. 9 is the figure of the lithium rechargeable battery 100A representing that one embodiment of the present invention is related to.
Figure 10 is the figure of the structure of negative electrode active material layer 243A representing this lithium rechargeable battery 100A.
Figure 11 is the evaluation electricity pool unit representing for sample A～C, the electricity after above-mentioned ratio A/B and charge and discharge cycles
The figure of the relation of resistance increment rate (%).
Figure 12 is to represent for negative electrode active material particle, the figure of the relation of 150 tap densities and peel strength.
Figure 13 is the figure representing 90 degree of stripping adhesive strength test methods.
Figure 14 is to schematically show to possess the non-aqueous secondary battery (vehicle traction that one embodiment of the present invention is related to
With battery) vehicle (automobile) side view.
Specific embodiment
Here, first, a configuration example of the lithium rechargeable battery as non-aqueous secondary battery is described.Then, fit
When with reference to said structure example, the lithium rechargeable battery that one embodiment of the present invention is related to is described.Should illustrate, play identical
The part of effect, position mark suitable identical symbol.In addition, each accompanying drawing is schematically described, reality might not be reflected
Thing.Each accompanying drawing is only to represent an example, does not limit the present invention in case of no particular description.
Fig. 1 represents lithium rechargeable battery 100.This lithium rechargeable battery 100 possesses rolled electrode bodies as shown in Figure 1
200 with battery container 300.Fig. 2 is the figure representing rolled electrode bodies 200.Fig. 3 is the III-III section representing in Fig. 2.
Rolled electrode bodies 200 have positive plate 220, negative plate 240 and distance piece 262,264 as shown in Figure 2.Positive plate
220th, negative plate 240 and distance piece 262,264 are the sheet material of banding respectively.
《Positive plate 220》
Positive plate 220 possesses positive electrode collector 221 and the positive electrode active material layer 223 of banding.Positive electrode collector 221 is permissible
Preferably use the metal forming of suitable positive pole.Positive electrode collector 221 for example can using having the width of regulation, thickness is general 15
μm banding aluminium foil.It is set with uncoated portion 222 along the unilateral edge part of the width of positive electrode collector 221.In figure
In example, as shown in figure 3, positive electrode active material layer 223 is maintained at the uncoated portion 222 except being set in positive electrode collector 221
The two sides of positive electrode collector 221 in addition.Positive electrode active material layer 223 comprises positive active material.Positive electrode active material layer 223
Formed by the anode mixture comprising positive active material is coated on positive electrode collector 221.
《Positive electrode active material layer 223 and positive active material particle 610》
Here, Fig. 4 is the sectional view of positive plate 220.Should illustrate, in the diagram, for clear and definite positive electrode active material layer
223 structure, the positive active material particle 610 in positive electrode active material layer 223, conductive material 620 and binding agent 630 are put
Schematically show greatly.As shown in figure 4, positive electrode active material layer 223 comprises positive active material particle 610, conductive material
620 and binding agent 630.
Positive active material particle 610 can be using the thing of the positive active material that can act as lithium rechargeable battery
Matter.If enumerating the example of positive active material particle 610, LiNiCoMnO can be enumerated2(lithium nickel cobalt manganese oxide),
LiNiO2(lithium nickelate), LiCoO2(cobalt acid lithium), LiMn2O4(LiMn2O4), LiFePO4Lithium transition-metals such as (LiFePO4s) aoxidizes
Thing.Here, LiMn2O4For example there is spinel structure.In addition, LiNiO2Or LiCoO2There is the rock salt structure of stratiform.Separately
Outward, LiFePO4For example there is olivine structural.The LiFePO of olivine structural4For example there is nano level particle.In addition, olivine
The LiFePO of structure4Can be coated to by carbon film further.
《Conductive material 620》
As conductive material 620, for example, it is possible to illustrate the material with carbon elements such as carbon dust, carbon fiber.As conductive material 620, can
To be used alone selected from one of this conductive material it is also possible to and with more than two kinds.As carbon dust, it is possible to use various
The carbon dusts such as white carbon black (for example, acetylene black, Audit For Process white carbon black, Graphon, white carbon black, graphite, Ketjen black), powdered graphite.
《Binding agent 630》
In addition, binding agent 630 makes positive active material particle 610 and conductive material contained by positive electrode active material layer 223
620 each particle is bondd or so that these particles is bondd with positive electrode collector 221.As above-mentioned binding agent 630, it is possible to use energy
Enough dissolving or scattered polymer in the solvent using.For example, in the anode mixture compositionss employing aqueous solvent, can
To preferably employ cellulose-based polymer (carboxymethyl cellulose (CMC), hydroxypropyl methyl cellulose (HPMC) etc.), fluorine resin
(for example, polyvinyl alcohol (PVA), politef (PTFE), tetrafluoraoethylene-hexafluoropropylene copolymer (FEP) etc.), rubber-like
Water such as (vinyl acetate co-polymer, styrene-butadiene-copolymer (SBR), acrylic acid modified SBR resins (SBR system latex) etc.)
Dissolubility or aqueous dispersion polymers.In addition, it may be preferred to adopt polymerization in the anode mixture compositionss employ nonaqueous solvent
Thing (Kynoar (PVDF), Vingon (PVDC), polyacrylonitrile (PAN) etc.).
《Viscosifier, solvent》
Positive electrode active material layer 223 is for example formed as follows, i.e. by making above-mentioned positive active material particle 610 He
Conductive material 620 is mixed into anode mixture obtained from paste (Slurries) in a solvent, and coats positive electrode collector 221,
It is dried, roll and formed.Now, as the solvent of anode mixture, aqueous solvent and nonaqueous solvent all can use.As non-
The preferred example of aqueous solvent, can enumerate METHYLPYRROLIDONE (NMP).The polymer illustrating as above-mentioned binding agent 630
Material, except the function as binding agent, can also be to play as the viscosifier of anode mixture and the function of other additives
Purpose and use.
It is (typical that the shared mass ratio in anode mixture is overall of positive active material is preferably general more than 50wt%
It is 50～95wt%), generally more preferably general 70～95wt% (such as 75～90wt%).In addition, conductive material is in positive pole
During mixture is overall, shared ratio can be, for example, general 2～20wt% it is often preferred that general 2～15wt%.Using viscous
In the composition of mixture, the shared ratio in anode mixture is overall of binding agent can be, for example, general 1～10wt% it is usually preferred to
For general 2～5wt%.
《Negative plate 240》
As shown in Fig. 2 negative plate 240 possesses negative electrode collector 241 and the negative electrode active material layer 243 of banding.Negative pole collection
Electric body 241 can be well using the metal forming of suitable negative pole.This negative electrode collector 241 is using width, the thickness with regulation
Copper Foil for general 10 μm of banding.It is set with uncoated portion in the width one side of negative electrode collector 241 along edge part
242.Negative electrode active material layer 243 is formed at the negative pole current collection in addition to the uncoated portion 242 being set in negative electrode collector 241
The two sides of body 241.Negative electrode active material layer 243 is maintained at negative electrode collector 241, including at least negative electrode active material.Negative pole is lived
Property material layer 243 is that the cathode agent comprising negative electrode active material is coated on negative electrode collector 241 and forms.
《Negative electrode active material layer 243》
Fig. 5 is the sectional view of the negative plate 240 of lithium rechargeable battery 100.As shown in figure 5, negative electrode active material layer 243
Comprise negative electrode active material particle 710, viscosifier (omitting diagram), binding agent 730 etc..In Figure 5, for clear and definite negative electrode active
The structure of material layer 243, the negative electrode active material particle 710 in negative electrode active material layer 243 is amplified signal with binding agent 730
Property ground represent.
《Negative electrode active material particle 710》
As negative electrode active material particle 710, can be not particularly limited using in the past for lithium rechargeable battery
One of material or more than two kinds.For example, it is possible to enumerate the particle that at least a portion comprises graphite-structure (layer structure)
The material with carbon element (carbon particle) of shape.More specifically, negative electrode active material can be such as native graphite, use amorphous material with carbon element
The native graphite of coating, graphite (graphite), difficult graphitization carbonaceous (hard carbon), easy graphitization carbonaceous (soft carbon) or by it
The material with carbon element that combines.Should illustrate, here, negative electrode active material particle 710 illustrates using so-called flaky graphite
Situation, negative electrode active material particle 710 is not limited to illustrated example.
As other negative electrode active materials, can be for example using Si, Ge, Sn, Pb, Al, Ga, In, As, Sb, Bi etc. as
Metallic compound (preferably metal-oxide) of composition metal element etc..In addition, as negative electrode active material particle, acceptable
Using LTO (lithium titanate).In addition, be for the negative electrode active material being made up of metallic compound, for example, it is possible to will by carbon coating
The surface of metallic compound is fully coating, makes the coccoid of excellent electric conductivity and uses.Now, negative electrode active material layer is permissible
Do not contain conductive material it is also possible to the containing ratio of minimizing conductive material compared with the past.These negative electrode active materials additional
The forms such as mode, particle diameter suitably can select according to desired characteristic.
《Viscosifier, solvent》
Negative electrode active material layer 243 is for example formed as follows, i.e. makes above-mentioned negative electrode active material particle 710 and glues
Mixture 730 is mixed into cathode agent obtained from paste (Slurries) in solvent, and coats negative electrode collector 241, is done
Dry, rolling and formed.Now, as the solvent of cathode agent, aqueous solvent and nonaqueous solvent all can use.As nonaqueous solvent
Preferred example, METHYLPYRROLIDONE (NMP) can be enumerated.Binding agent 730 can be used as aftermentioned negative electrode active material
Layer 243A binding agent 730 and illustrate polymeric material.In addition, the binding agent 630 as above-mentioned positive electrode active material layer 223
And illustrate polymeric material in addition to the function as binding agent, can also using play as anode mixture or cathode agent
Viscosifier and the purpose of function of other additives and use.
《Distance piece 262,264》
As shown in Figure 1 or 2, distance piece 262,264 is the part of interval positive plate 220 and negative plate 240.In this example
In, distance piece 262,264 is made up of the sheet material of the banding of the Rack with multiple small holes.Distance piece 262,264
As the distance piece of single layer structure being made up of porous polyolefin system resin or the distance piece of stepped construction can be used.In this example
In, as shown in Figures 2 and 3, the width b1 of negative electrode active material layer 243 is more slightly wider than the width a1 of positive electrode active material layer 223.This
Outward, width c1, c2 of distance piece 262,264 more slightly wider than the width b1 of negative electrode active material layer 243 (c1, c2 ＞ b1 ＞ a1).
Should illustrate, in the example shown in Fig. 1 and Fig. 2, distance piece 262,264 is made up of the part of lamellar.Distance piece
As long as the 262,264 allowing electrolysis while positive electrode active material layer 223 and negative electrode active material layer 243 can be insulated
The part of the movement of matter.Therefore, it is not limited to the part of lamellar.Distance piece 262,264 can replace lamellar part and by
For example it is formed at the layer structure of the particle with insulating properties on the surface of positive electrode active material layer 223 or negative electrode active material layer 243
Become.Here, as the particle with insulating properties, can be by inorganic filler (for example, metal-oxide, the gold with insulating properties
Belong to the filler such as hydroxide) or there is the resin particle (for example, particle such as polyethylene, polypropylene) of insulating properties constitute.
As shown in Figures 2 and 3, in this rolled electrode bodies 200, positive plate 220 and negative plate 240 are to clip distance piece
262nd, 264 state is overlapping in the way of positive electrode active material layer 223 is opposed with negative electrode active material layer 243.More specifically,
In rolled electrode bodies 200, positive plate 220, negative plate 240 and distance piece 262,264 are with positive plate 220, distance piece 262, negative
Pole piece 240, the order overlap of distance piece 264.
In addition, now, positive electrode active material layer 223 and negative electrode active material layer 243 are to clip the shape of distance piece 262,264
State is opposed.And, unilateral in positive electrode active material layer 223 part opposed with negative electrode active material layer 243 protrudes positive pole collection
Do not form the part (uncoated portion 222) of positive electrode active material layer 223 in electric body 221.With the side protruding this uncoated portion 222
Contrary side, the part (uncoated portion 242) not forming negative electrode active material layer 243 in negative electrode collector 241 is protruded.
《Battery container 300》
In addition, in this example embodiment, as shown in figure 1, battery container 300 is so-called square battery container, possesses container
Main body 320 and lid 340.Container body 320 has bottom four square tube shape, is the flat box of one side (above) opening
Container.Lid 340 is mounted to the opening (opening above) of this container body 320 to block the part of this opening.
For in vehicle-mounted secondary cell, in order to improve the fuel efficiency of vehicle, it is desirable to increase weight energy efficiency is (often single
The capacity of the battery of position weight).In this embodiment, the container body 320 constituting battery container 300 is adopted with lid 340
The light metals such as aluminum, aluminium alloy.Thus, it is possible to improve weight energy efficiency.
Battery container 300 has the inner space of flat rectangle as the space housing rolled electrode bodies 200.Separately
Outward, as shown in figure 1, the flat inner space of battery container 300 width degree compared with rolled electrode bodies 200 is slightly wider.Real at this
Apply in mode, battery container 300 possesses the lid of the container body 320 having bottom four square tube shape and the opening of blocking container main body 320
Body 340.In addition, the lid 340 of battery container 300 is provided with electrode terminal 420,440.Electrode terminal 420,440 insertion batteries
Housing 300 (lid 340) and expose the outside of battery container 300.In addition, lid 340 is provided with liquid injection hole 350 and relief valve 360.
As shown in Fig. 2 rolled electrode bodies 200 bend in the extruding of orthogonal with a wireline reel WL direction flat.In Fig. 2
In shown example, the uncoated portion 222 of positive electrode collector 221 and the uncoated portion 242 of negative electrode collector 241 are respectively at interval
The both sides of part 262,264 are spirally exposed.As shown in fig. 6, in this embodiment, assemble in uncoated portion 222,242
Between part 224,244 and leading section 420a, 440a welding with electrode terminal 420,440.Now, due to each material not
With electrode terminal 420 uses such as ultrasonic fusing with the welding of positive electrode collector 221.In addition, electrode terminal 440 and negative pole
The welding of collector 241 is for example using electric resistance welding.Here, Fig. 6 is the uncoated portion 222 representing rolled electrode bodies 200
(242) mid portion 224 (244) and the side view at the welding position of electrode terminal 420 (440), are the VI-VI sections of Fig. 1
Figure.
Rolled electrode bodies 200 with extrude bend to flat state be installed on be fixed on lid 340 electrode terminal 420,
440.As shown in figure 1, above-mentioned rolled electrode bodies 200 are housed in the flat inner space of container body 320.Container body 320
Clogged by lid 340 after housing rolled electrode bodies 200.The interface 322 (with reference to Fig. 1) of lid 340 and container body 320 is for example
Carried out welding to seal by laser welding.Like this, in this example embodiment, rolled electrode bodies 200 are by being fixed on lid 340
The electrode terminal 420,440 of (battery container 300) and in battery container 300 determine position.
《Electrolyte》
Then, from be located at the liquid injection hole 350 of lid 340 to battery container 300 in inject electrolyte.Electrolyte using not with
Water is the so-called nonaqueous electrolytic solution of solvent.For example, electrolyte can use the mixing in ethylene carbonate and diethyl carbonate
Solvent (for example, volume ratio 1：1 about mixed solvent) in about 1mol/ rise concentration contain LiPF6Electrolyte.Injection electricity
After solution liquid, by installing metal seal cap 352 (for example passing through welding) in liquid injection hole 350, battery container 300 is close
Envelope.Should illustrate, electrolyte is not limited to the electrolyte illustrating here.For example, it is possible to suitable be used for lithium ion two using conventional
The nonaqueous electrolytic solution of primary cell.
《Emptying aperture》
Here, positive electrode active material layer 223 is for example in the particle of positive active material particle 610 and conductive material 620
Between etc. there is the small gap 225 (with reference to Fig. 4) that be referred to as cavity.Above-mentioned positive electrode active material layer 223 small
Gap in can immerse electrolyte (omit diagram).In addition, negative electrode active material layer 243 is for example in negative electrode active material particle
There is between 710 particle etc. the small gap 245 (with reference to Fig. 5) that be referred to as cavity.Here, by above-mentioned gap
225th, 245 (empty) be properly termed as " emptying aperture ".In addition, as shown in Fig. 2 for rolled electrode bodies 200, along the two of wireline reel WL
Side, uncoated portion 222,242 winds curl.In the both sides 252,254 along above-mentioned wireline reel WL, electrolyte can be never
The gap immersion of coated portion 222,242.Therefore, in the inside of lithium rechargeable battery 100, electrolyte permeability is in positive electrode active material
Matter layer 223 and negative electrode active material layer 243.
《Air relief path》
In addition, in this example embodiment, the flat internal space ratio of this battery container 300 is deformed into flat rolled electrode bodies
200 is slightly wider.The both sides of rolled electrode bodies 200, are provided with gap 310,312 between rolled electrode bodies 200 and battery container 300.
This gap 310,312 becomes air relief path.For example, in the case of there is overcharge etc., if lithium rechargeable battery 100
Temperature anomaly raises, then electrolyte is decomposed and extremely produces gas sometimes.In this embodiment, the abnormal gas producing leads to
Cross the rolled electrode bodies 200 of both sides of rolled electrode bodies 200 and the gap 310,312 of battery container 300 and to relief valve 360
One side moves, outside relief valve 360 is vented to battery container 300.
In above-mentioned lithium rechargeable battery 100, positive electrode collector 221 and negative electrode collector 241 pass through insertion battery case
The electrode terminal 420,440 of body 300 is electrically connected with outside device.Hereinafter, with the lithium ion secondary during electric discharge when illustrating to charge
The action of battery 100.
《Work during charging》
Fig. 7 schematically shows the state during charging of above-mentioned lithium rechargeable battery 100.When charging, as Fig. 7 institute
Show, the electrode terminal 420,440 (with reference to Fig. 1) of lithium rechargeable battery 100 is connected to charger 290.By charger 290
Effect, during charging, the positive active material from positive electrode active material layer 223 releases lithium ion (Li) to electrolyte 280.Separately
Outward, release electric charge from positive electrode active material layer 223.The electric charge released passes through conductive material (omitting diagram) and is sent to positive pole current collections
Body 221, and then, conveyed to negative plate 240 by charger 290.In addition, store electric charge in negative plate 240, and electrolyte
Lithium ion (Li) in 280 is absorbed by the negative electrode active material in negative electrode active material layer 243, and is stored.
《Action during electric discharge》
Fig. 8 schematically shows the state during electric discharge of above-mentioned lithium rechargeable battery 100.As shown in figure 8, during electric discharge,
From negative plate 240 to positive plate 220 delivered charge, and it is stored in the lithium ion of negative electrode active material layer 243 and is released to electrolysis
Liquid 280.In addition, entering the positive active material in positive electrode active material layer 223 in the lithium ion in positive pole, electrolyte 280.
Like this, in the discharge and recharge of lithium rechargeable battery 100, via electrolyte 280, lithium ion is in positive electrode active material
Come and go between matter layer 223 and negative electrode active material layer 243.In addition, when charging, electric charge passes through conduction material from positive active material
Expect to convey to positive electrode collector 221.On the other hand, in electric discharge, electric charge is just returned by conductive material from positive electrode collector 221
Pole active substance.
Think that, when charging, the movement of lithium ion and the movement of electronics are more smooth, are more capable of effective and quickly fill
Electricity.Think that, in electric discharge, the movement of lithium ion and the movement of electronics are more smooth, the resistance of battery reduces, and discharge capacity increases, battery
Output improve.
《Other battery shape》
Should illustrate, an example of above-mentioned expression lithium rechargeable battery.Lithium rechargeable battery is not limited to above-mentioned shape
State.In addition, the same electrode slice being coated with electrode composition in metal forming is additionally used for various battery shape.For example, as it
His battery shape is it is known that cylinder battery or laminated-type battery etc..Cylinder battery is to house in the battery container of cylinder type
The battery of rolled electrode bodies.In addition, laminated-type battery is the battery being laminated positive plate and negative plate via distance piece.
Hereinafter, the lithium rechargeable battery of the non-aqueous secondary battery as one embodiment of the present invention is described.Should
Illustrate, here, play the part of phase same-action with above-mentioned lithium rechargeable battery 100 or position suitably uses identical symbol
Number, as needed, the figure with reference to above-mentioned lithium rechargeable battery 100 to illustrate.
《Lithium rechargeable battery 100A》
Fig. 9 is to represent lithium rechargeable battery 100A as the non-aqueous secondary battery proposing here.Figure 10 represents
The structure of the negative electrode active material layer 243A of above-mentioned lithium rechargeable battery 100A.
As shown in figure 9, lithium rechargeable battery 100A possesses negative electrode collector 241A and is maintained at negative electrode collector 241A
Negative electrode active material layer 243A.As shown in Figure 10, negative electrode active material layer 243A comprises negative electrode active material particle 710 and glues
Mixture 730.In this embodiment, binding agent 730 comprises elastomeric adhesive or has the resin of binding agent function (for example,
Acrylic adhesive, imide series binding agent).And, elastomeric adhesive or there is the resin of binding agent function wrap in a large number
It is contained in the near surface of negative electrode active material layer 243A in negative electrode active material layer 243A.According to above-mentioned non-aqueous secondary battery,
The releasing of lithium ion in negative electrode active material layer 243A, the response speed of occlusion can be maintained higher.Therefore, particularly
Under -15 DEG C about of low temperature environment, the resistance increment rate after charge and discharge cycles can be suppressed relatively low.Hereinafter, in more detail
Above-mentioned non-aqueous secondary battery is described.
《Negative electrode active material layer 243A》
The resin that negative electrode active material layer 243A comprises elastomeric adhesive or has binding agent function.Glue as rubber series
Mixture, can illustrate SBR styrene butadiene rubberses (SBR).In addition, as the resin with binding agent function, for example, it is possible to example
Show acrylic adhesive, acid imide binding agent, poly(ethylene oxide) (PEO：Polyethylene oxide), polyethylene (PE).
SBR, PEO, PE are the binding agent that can be scattered in aqueous solvent.As imide series binding agent, can enumerate can act as non-
The binding agent of the imide series of the binding agent of negative electrode active material layer 243A of aqoue seconary battery.Glue as above-mentioned imide series
Mixture, for example, can illustrate polyamidoimide.
As shown in Figure 10, in this embodiment, viscous as elastomeric adhesive or the resin with binding agent function
Mixture 730 is included in the near surface A1 of the negative electrode active material layer 243A in negative electrode active material layer 243A in a large number.That is, negative
The near surface A1 of pole active material layer 243A, compared with the other parts of negative electrode active material layer 243A, elastomeric adhesive
Or there is the mass concentration height of the resin of binding agent function.
Here, the near surface A1 of negative electrode active material layer 243A for example can specify that into negative electrode active material layer 243A
In from a surface to 1/4 thickness region.Now, the rubber series contained by the near surface A1 of negative electrode active material layer 243A are glued
Mixture carries out total mass concentration A and by negative electrode active material layer 243A except surface with the resin with binding agent function
Nearby the partly contained elastomeric adhesive of A1 and the resin with binding agent function carry out the ratio A/ of total mass concentration B
B can be general 2.0～3.8 (2.0≤(A/B)≤3.8).
That is, in this lithium rechargeable battery 100A, elastomeric adhesive or have the resin of binding agent function all over point
It is distributed in the near surface A1 of negative electrode active material layer 243A.As described above, the near surface A1 by negative electrode active material layer 243A
When being specified in negative electrode active material layer 243A the region from a surface to 1/4 thickness, and by negative electrode active material layer 243A's
Except the partly contained elastomeric adhesive of near surface A1 with there is the resin of binding agent function to carry out total quality dense
The ratio A/B of degree B is general 2.0～3.8.This represents elastomeric adhesive and has the resin of binding agent function in negative electrode active material
The near surface A1 and negative electrode active material layer 243A of matter layer 243A is except becoming general 2 times compared with the part of near surface A1
～3.8 times and exist in a large number.
In lithium rechargeable battery 100A, elastomeric adhesive is most as mentioned above with the resin with binding agent function
It is present in the near surface A1 of negative electrode active material layer 243A.Therefore, it is possible to maintain higher in negative electrode active material layer 243A
The releasing of lithium ion, the response speed of occlusion.Particularly in -15 DEG C about of low temperature environment, repeated with high-speed and continuous
Carry out in the purposes of discharge and recharge, lithium rechargeable battery 100A can lower maintain resistance.
The present inventor is speculated as follows to the effect above.
Generally, elastomeric adhesive and the resin with binding agent function will not be partial to negative electrode active as mentioned above in a large number
The near surface A1 of material layer 243A.Now, on the surface of negative electrode active material layer 243 (with reference to Fig. 7 or Fig. 8), release or inhale
Stay the position of lithium ion uneven.That is, the surface of negative electrode active material layer 243A exists and is easier to release or occlusion lithium ion
Position and being difficult to release or occlusion lithium ion position.Like this, if existed on the surface of negative electrode active material layer 243A
Occlusion, the inequality of releasing lithium ion, then the positive electrode active material layer 223 (with reference to Fig. 7 or Fig. 8) resisting also produces and easily carries out electricity
Pond reaction position and be difficult to position.In addition, if there is the suction of lithium ion on the surface of negative electrode active material layer 243A
The inequality stay, released, then become principal element overall as battery and that resistance increases.Table in negative electrode active material layer 243
Face can be formed lithium ion occlusion, release uneven the reason also correctly do not know.
In above-mentioned lithium rechargeable battery 100A, elastomeric adhesive is inclined in a large number with the resin with binding agent function
To in the near surface A1 of negative electrode active material layer 243A.Now, by being partial to the table of negative electrode active material layer 243A in a large number
The face elastomeric adhesive of A1 and the resin with binding agent function nearby, in negative electrode active material layer 243A, from negative electrode active
The lithium ion that material particle 710 is released is rectified.Additionally, it is believed that in the surface of negative electrode active material layer 243A, occlusion lithium ion
Point also generally uniform distribution.Thus, eliminate the occlusion of the lithium ion on surface of negative electrode active material layer 243A, release not
All, on the surface of negative electrode active material layer 243A, than the occlusion, the releasing that relatively evenly carry out lithium ion.If in negative electrode active
The surface of material layer 243A, substantially evenly carries out occlusion, the releasing of lithium ion, then in the positive electrode active material layer 223 of antagonism
(with reference to Fig. 7 or Fig. 8) also more uniformly carries out cell reaction.Overall accordingly, as battery, resistance is suppressed relatively low.Should
Illustrate, the imagination based on the present inventor for the above-mentioned effect.
Above-mentioned negative electrode active material layer 243A is for example formed as follows, i.e. make negative electrode active material particle 710 and bonding
Agent 730 is mixed into cathode agent obtained from paste (Slurries) in a solvent, coats negative electrode collector 241, and is done
Dry, roll and formed.In above-mentioned forming method, migrate in drying process.By migration, elastomeric adhesive and tool
How many resins having binding agent function moves to the near surface A1 of negative electrode active material layer 243A.But, generally live in negative pole
The near surface A1 of property material layer 243A, elastomeric adhesive with there is the resin of binding agent function compared to negative electrode active material
The other parts of layer 243A, do not reach general 2 times～3.8 times.
In this embodiment, make and negative electrode active material particle 710 and binding agent 730 are mixed into paste in a solvent
The cathode agent of (Slurries).Now, solvent uses water solvent, and with respect to negative electrode active material particle 710 and bonding
Agent 730 increases the amount of solvent.Additionally, in drying process, rising high dry temperature.Thus, easily produce migration, in negative electrode active
The near surface A1 of material layer 243A, elastomeric adhesive and the resin with binding agent function and negative electrode active material layer 243A
Other parts be in a ratio of general 2 times～3.8 times.
More specifically, in this embodiment, negative electrode active material particle 710, the CMC as viscosifier and binding agent
730 mass ratio is negative electrode active material particle 710：CMC：Binding agent 730=98：1：1.As the solvent of cathode agent,
Add pure water.Now, use Brookfield viscometer as viscometer, with room temperature (here for 25 DEG C), the viscosity of cathode agent
Mode for general 3000mPa s (20rpm) adjusts the cathode agent of coating.In addition, in drying process, after coating, immediately
Put into and be dried in atmosphere, promote migration.
Should illustrate, here, strength produces migration, in the near surface A1 of negative electrode active material layer 243A, rubber series
Binding agent is in a ratio of general 2 times～3.8 with the other parts of the resin and negative electrode active material layer 243A with binding agent function
Times.The formation of negative electrode active material layer 243A is not limited to said method.
Here, as the method forming negative electrode active material layer 243A, exemplified with the strong method producing migration, but shape
The method becoming negative electrode active material layer 243A is not limited to the method.As the additive method forming negative electrode active material layer 243A,
For example, it is possible to fraction time is coated with cathode agents to form negative electrode active material layer 243A for (in other words, at least 2 times).Now,
In the cathode agent of near surface applied, that negative electrode active material layer 243A can be formed after 2 times, rubber series can be improved
The ratio of binding agent and the resin with binding agent function.
Like this, in this embodiment, in the near surface A1 of negative electrode active material layer 243A, make elastomeric adhesive
It is in a ratio of general 2 times～3.8 times with the other parts of the resin and negative electrode active material layer 243A with binding agent function.
Here, in negative electrode active material layer 243A, how elastomeric adhesive and the resin with binding agent function divide
Cloth can based on formed negative electrode active material layer 243A cross-sectional SEM image, for example utilize EDX analysis (energy dispersion type X penetrates
Line analysis：Energy Dispersive Analysis of X-ray (EDAX)) carrying out.Thus, it is possible to be determined based on this
In negative electrode active material layer 243A, how elastomeric adhesive and the resin with binding agent function are distributed.
For example, when comprising the SBR as elastomeric adhesive in negative electrode active material layer 243A, by SBR with bromine (Br)
After dyeing, using energy dispersion-type X-ray analysis, the distribution of the Br in investigation negative electrode active material layer 243A.Thus, it is possible to
Know how SBR is distributed in negative electrode active material layer 243A.
Here, as EDX analytical equipment (Energy Dispersive X-ray Analyzer), employ a plant formula meeting
The MACHS200 of Shimadzu Seisakusho Ltd. of society.During the distribution of research SBR, the condition of EDX analysis (EDX quantitative analyses) for example can be as
Under.
Accelerating potential：15kv；
Operating distance：WD=about 10mm；
Detector current：60nA～70nA；
Multiplying power：1000 times；
It is not limited to SBR, the distribution of the binding agent in negative electrode active material layer can be investigated with EDX analysis.Here,
Elastomeric adhesive contained by the near surface A1 of negative electrode active material layer 243A is carried out with the resin with binding agent function
Total mass concentration A with by negative electrode active material layer 243A except the partly contained elastomeric adhesive of near surface A1
The ratio A/B carrying out total mass concentration B with the resin with binding agent function can be general 2.0～3.8 (2.0≤(A/B)
≤3.8).Thus, for example, it is possible to suppress continuously repeating the resistance increment rate after the charge and discharge cycles charging and discharging
Relatively low.
《Evaluation electricity pool unit》
Here, it is made for the different evaluation electricity pool unit of above-mentioned ratio A/B.And, for each evaluation electricity pool list
Unit, have rated the resistance increment rate after the charge and discharge cycles of regulation.Here, evaluation electricity pool unit is by 18650 type battery lists
Unit is constituted.In addition, evaluation electricity pool unit has prepared the different sample A～C of structure of negative electrode active material layer.Hereinafter, explanation
Sample A, and then sample B, C are described successively.
《The positive pole of evaluation electricity pool unit》
It is prepared for anode mixture when forming the positive electrode active material layer in positive pole.Here, anode mixture employs work
Lithium transition-metal oxide (LiNi for the ternary system of positive active material1/3Co1/3Mn1/3O2), as conductive material acetylene
Black (AB), the Kynoar (PVDF) as binding agent.Here, the matter of positive active material, conductive material and binding agent
Amount ratio is positive active material：Conductive material：Binding agent=91：6：3.By by these positive active materials, conductive material, viscous
Mixture is mixed with ion exchange water and is prepared for anode mixture.Then, two sides anode mixture being coated positive electrode collector is simultaneously
It is dried.Here, employ the aluminium foil (15 μm of thickness) as positive electrode collector.Thus, made in positive electrode collector
Two sides possess the positive pole (positive plate) of positive electrode active material layer.Positive plate is made by rolling with roll squeezer after the drying
Its thickness is 110 μm.To the coating weight of positive electrode collector, anode mixture is set to that anode mixture is dried after, in positive electrode collector
Per unit area, positive electrode active material layer is 25mg/cm2.
《The negative pole (sample A) of evaluation electricity pool unit》
Here, first, sample A is illustrated.In sample A, cathode agent employs respectively：As negative electrode active
The lepidiod native graphite of material, the carboxymethyl cellulose (CMC) as viscosifier, binding agent.In sample A, binding agent
SBR styrene butadiene rubberses (SBR) as elastomeric adhesive are used.
Here, in sample A, the mass ratio of negative electrode active material, viscosifier (CMC) and binding agent (SBR) is negative pole
Active substance：CMC：SBR=98：1：1.By these negative electrode active materials, CMC, SBR are mixed with ion exchange water and prepare
Cathode agent.Then, cathode agent is coated the two sides of negative electrode collector and be dried.Here, employ conduct
The Copper Foil (10 μm of thickness) of negative electrode collector.Thus, made and possessed negative electrode active material layer on the two sides of negative electrode collector
Negative pole (negative plate).Negative plate is made its thickness be 100 μm by rolling with roll squeezer after the drying.Thus, it is formed at
The thickness of the negative electrode active material layer on the two sides of negative electrode collector is respectively 45 μm.Cathode agent is to the coating weight of negative electrode collector
It is set as that in the per unit area of negative electrode collector, negative electrode active material layer becomes 13mg/cm after cathode agent is dried2.
《The distance piece of evaluation electricity pool unit》
As distance piece, employ the porous chipses of the three-decker (PP/PE/PP) by polypropylene (PP), polyethylene (PE)
The distance piece constituting.
《The assembling of evaluation electricity pool unit》
Using the negative pole of above-mentioned making, positive pole and distance piece, construct the 18650 type battery unit (lithium ions for test
Battery).Here, made with the volume of drum positive plate and negative plate being laminated and being wound across the state of distance piece
Around electrode body.And, rolled electrode bodies are contained in the battery container of drum, nonaqueous electrolytic solution are carried out fluid injection and seals
Mouthful, construct evaluation electricity pool unit.Here, as nonaqueous electrolytic solution, employ by ethylene carbonate (EC), carbonic acid two
Methyl ester (DMC) and ethyl methyl carbonate (EMC) volume ratio (EC to specify：DMC：EMC=3：4：3) dissolve in the solvent mixing
There is the LiPF of the 1mol/L as lithium salts6Electrolyte.
Hereinafter, to sample A～C, it is described in detail respectively.
《Sample A；Binding agent：SBR, the thickness of negative electrode active material layer：45μm》
As described above, in sample A, as the binding agent of negative electrode active material layer, being used as elastomeric adhesive
SBR styrene butadiene rubberses (SBR).In addition, being formed at the thickness of the negative electrode active material layer on the two sides of negative electrode collector respectively
For 45 μm.
Here, to above-mentioned sample A, prepared the matter of the SBR contained by near surface A1 changing negative electrode active material layer
Amount concentration A and negative electrode active material layer are more than A/B except mass concentration B of the partly contained SBR of near surface A1
Individual evaluation electricity pool unit.And, to each evaluation electricity pool unit, determine the resistance increment rate after continuous discharge and recharge.
Should illustrate, be by cathode agent during adjustment formation negative electrode active material layer than A/B, suitably adjust further
The condition of drying process, thus adjust the degree of migration.In addition, here, the near surface A1 regulation of negative electrode active material layer
Be in negative electrode active material layer from a surface to 1/4 thickness region.This point is to sample B, C similarly.
《Sample B；Binding agent：PVDF, the thickness of negative electrode active material layer：45μm》
For sample B, as the binding agent contained by negative electrode active material layer, SBR is replaced to employ PVDF.Use
During PVDF, solvent during adjustment cathode agent employs the METHYLPYRROLIDONE (NMP) as non-water solvent.In addition,
Negative electrode active material is negative electrode active material with the mass ratio of binding agent (PVDF)：PVDF=98：2.Now, as binding agent,
Except by using the item caused by PVDF, generally constituting with the sample identical employing SBR.
For above-mentioned sample B, the quality having prepared the PVDF contained by near surface A1 changing negative electrode active material layer is dense
Multiple the commenting of the ratio A/B of degree A and negative electrode active material layer mass concentration B except the partly contained PVDF of near surface A1
Valency battery unit.And, for each evaluation electricity pool unit, determine the resistance increment rate after continuous discharge and recharge.
《Sample C；Binding agent：SBR, the thickness of negative electrode active material layer：75μm》
In addition, having prepared to make the thickness of negative electrode active material layer on the two sides of negative electrode collector to essentially become 75 μm of side
The sample that formula is formed.Cathode agent is set to after cathode agent is dried to the coating weight of negative electrode collector, in negative electrode collector
Per unit area, negative electrode active material layer be 20mg/cm2.
Here, for above-mentioned sample C, prepared to change the SBR's contained by near surface A1 of negative electrode active material layer
The ratio A/B's of mass concentration A and negative electrode active material layer mass concentration B except the partly contained SBR of near surface A1
Multiple evaluation electricity pool units.And, to each evaluation electricity pool unit, determine the resistance increment rate after continuous discharge and recharge.
《Compare A/B》
Here, for each sample, obtain the matter of the binding agent contained by near surface A1 of negative electrode active material layer 243A
The ratio of amount concentration A and negative electrode active material layer 243A mass concentration B except the partly contained binding agent of near surface A1
A/B.This can be measured as said above with EDX analysis (EDAX) than A/B.
《Resistance increment rate (the resistance increment rates (%) after charge and discharge cycles)》
Here, for each evaluation electricity pool unit of sample A～C, after implementing the regulation of regulation, it is adjusted to SOC
60%, measure initial stage resistance V1.Then, under -15 DEG C of temperature environment, continuously repeat charge and discharge with the charge and discharge cycles of regulation
Electricity, measures resistance (resistance V2 after circulation) again with after charge and discharge cycles before this charge and discharge cycles.Here, resistance increment rate
V is the ratio (V2/V1) of resistance V2 and initial stage resistance V1 after circulation.
《Adjust》
Adjust here and carried out by following steps 1,2.
Step 1：Reached after 4.1V with the constant current charge of 1C, rest 5 minutes.
Step 2：After step 1, carry out 1.5 hours charging with constant-potential charge, rest 5 minutes.
In above-mentioned regulation, occur need to react and produce gas because the initial stage charges.In addition, in negative electrode active material
Layer etc. forms the envelope needing and is formed.
《The mensure of rated capacity》
After above-mentioned regulation, rated capacity is measured to evaluation electricity pool unit.The mensure of rated capacity pass through following steps 1～
3 are measured.Should illustrate, here in order that the impact that brings of temperature is constant, rated capacity is in the temperature ring of 25 DEG C of temperature
Measure under border.
Step 1：After the constant current electric discharge of 1C reaches 3.0V, discharged 2 hours with constant voltage electric discharge, then,
Rest 10 seconds.
Step 2：After the constant current charge of 1C reaches 4.1V, charged 2.5 hours with constant-potential charge, so
Afterwards, rest 10 seconds.
Step 3：After the constant current electric discharge of 0.5C reaches 3.0V, discharged 2 hours with constant voltage electric discharge, then,
Rest 10 seconds.
Here, by the discharge capacity the electric discharge till constant current is discharged to constant voltage electric discharge in step 3
(CCCV discharge capacity) is as " rated capacity ".
《SOC adjusts》
SOC adjustment is adjusted by the step of following 1,2.Here, SOC adjusts in above-mentioned regulation operation and specified appearance
Carry out after the mensure of amount.In addition, here, in order that the impact that temperature is brought is constant, enter under 25 DEG C of temperature environment
Row SOC adjusts.
Step 1：Start to be charged with the constant current of 1C from 3V, reach general the 60% of rated capacity charged state
(SOC 60%).
Step 2：After step 1, carry out constant-potential charge 2.5 hours.
Thus, evaluation electricity pool unit may be adjusted to the charged state specifying.Should illustrate, here, describe by
SOC is adjusted to 60% situation, by changing the charged state in step 1, can be adjusted to arbitrary charged state.For example,
When being adjusted to SOC 80%, in step 1, the charged state (SOC of evaluation electricity pool unit for rated capacity 80% can be made
80%).
《Charge and discharge cycles》
Here, first, evaluation electricity pool unit is adjusted to SOC 60%.And, 1 time of charge and discharge cycles circulation by
Discharged 10 seconds with the constant current of 30C and constituted with the constant current charge 1 minute (60 seconds) of 5C.In addition, above-mentioned electric discharge with
Between charging, rest 10 minutes respectively.Here, when charge and discharge cycles are that often above-mentioned 1 time circulation is carried out 500 circulation, will comment
Valency battery unit is adjusted to SOC 60%, carries out 3000 circulations.
《IV resistance measurement》
Here, measure resistance after initial stage resistance and the circulation after charge and discharge cycles before charge and discharge cycles.Resistance IV
Resistance is evaluated.The mensure of resistance is under 25 DEG C of temperature environment, respectively evaluation electricity pool unit is adjusted to SOC 60%.And
And, after resting 10 minutes, evaluation electricity pool unit is discharged 10 seconds (CC electric discharge) with the constant current of 30C.Here, during electric discharge
Lower voltage limit be 3.0V.
In addition, Figure 11 is the evaluation electricity pool unit to each sample A～C represent above-mentioned ratio A/B and charge and discharge cycles after
Resistance increment rate (%) relation.Here, for the evaluation electricity pool unit of sample A, marked and drawed with " ◇ ", for sample B
Evaluation electricity pool unit, marked and drawed with " △ ", for the evaluation electricity pool unit of sample C, marked and drawed with " ".
《Sample A》
Sample A is binding agent SBR being used as negative electrode active material layer, and the thickness of negative electrode active material layer is general 45
μm.In fig. 11, the evaluation electricity pool unit of sample A is marked and drawed with " ◇ " and is illustrated.Now, in sample A, negative electrode active material layer
Mass concentration A of the SBR contained by near surface A1 and negative electrode active material layer the partly contained SBR except near surface
The ratio A/B of mass concentration B be when general 2.0～3.8 (2.0≤(A/B)≤3.8) it can be seen that electricity after charge and discharge cycles
The trend that resistance increment rate (%) maintains relatively low.If above-mentioned than A/B be less than 2.0, or above-mentioned than A/B be higher than 3.8, then have charge and discharge
The trend that resistance increment rate (%) after electricity circulation uprises.
《Sample B》
In addition, the binding agent contained by the negative electrode active material layer of sample B is PVDF, the thickness of negative electrode active material layer is 45
μm.In fig. 11, the evaluation electricity pool unit of sample B is marked and drawed with " △ " and is illustrated.Now, though above-mentioned than A/B for general 2.0～
3.8 (2.0≤(A/B)≤3.8), also can't see the trend that the resistance increment rate (%) after charge and discharge cycles maintains relatively low.
《Sample C》
Binding agent contained by the negative electrode active material layer of sample C is SBR, and the thickness of negative electrode active material layer is 75 μm.?
In Figure 11, the evaluation electricity pool unit of sample C is marked and drawed with " " and is illustrated.Now, for sample C, above-mentioned is general 2.0 than A/B
It is also possible to the becoming of maintaining relatively low of the resistance increment rate (%) after seeing charge and discharge cycles when～3.8 (2.0≤(A/B)≤3.8)
Gesture.
《The trend of the resistance increment rate (%) after charge and discharge cycles》
As shown in sample A, B, when using SBR as the binding agent of negative electrode active material layer, with negative electrode active material layer
Thickness unrelated, above-mentioned than A/B for general 2.0～3.8 (2.0≤(A/B)≤3.8) when, there is the resistance after charge and discharge cycles
The trend that increment rate (%) maintains relatively low.On the other hand, as shown in sample C, if the binding agent of negative electrode active material layer is
PVDF, even if the then above-mentioned electricity being general 2.0～3.8 (2.0≤(A/B)≤3.8) than A/B, also can't see after charge and discharge cycles
The trend that resistance increment rate (%) maintains relatively low.
As described above, the discharge and recharge in vehicle traction battery it is desirable under repeating at a high speed, negative electrode active material layer moment
Occlusion or the substantial amounts of lithium ion of releasing.Particularly, reduce in low temperature environment below -15 DEG C for the reaction of lithium ion, therefore, wish
Hope in such low temperature environment, the discharge and recharge under being smoothed out at a high speed.Binding agent accordingly, as negative electrode active material layer makes
With SBR, so with above-mentioned than A/B for the mode of general 2.0～3.8 (2.0≤(A/B)≤3.8), SBR deflection negative pole can be made
The near surface A of active material layer and be distributed.
Here, exemplified with the situation employing SBR as binding agent, but for other elastomeric adhesive, also can see
To same trend.In addition, in the opinion of the present inventor, being not only elastomeric adhesive, using, there is bonding
The resin of agent function, for example, acrylic adhesive (for example, poly(ethylene oxide) (PEO), polyethylene (PE)), imide series glue
In the case of mixture, it can be seen that same trend.Additionally, these elastomeric adhesive or have binding agent function resin excellent
Elect the binding agent that can be scattered in aqueous solvent as.Using the binding agent that can be scattered in aqueous solvent, above-mentioned be one than A/B
Determine during region (general 2.0～3.8 (2.0≤(A/B)≤3.8)) the resistance increment rate (%) it can be seen that after charge and discharge cycles
The trend maintaining relatively low.
Here, formed negative electrode active material layer operation in, be make the solvent in cathode agent increasing proportion and
And so that baking temperature is increased, compared with the past be susceptible to migrate situation.Therefore, above-mentioned than A/B become more than 2.0 greatly, glue
The near surface of negative electrode active material layer is partial to by mixture.Strongly migrate, in the near surface of negative electrode active material layer 243A
A1, elastomeric adhesive is in a ratio of probably with the other parts of the resin and negative electrode active material layer 243A with binding agent function
When 2 times～3.8 times, on the border of negative electrode active material layer 243A and negative electrode collector 241A, elastomeric adhesive with have viscous
The resin of mixture function tails off.It is therefore contemplated that the probability that negative electrode active material layer 243A peels off from negative electrode collector 241A becomes
High.
As shown in Figure 10, for lithium rechargeable battery 100A, as the binding agent of negative electrode active material layer 243A, such as
Upper described use elastomeric adhesive or the resin with binding agent function, and, above-mentioned be 2.0≤(A/B)≤3.8 than A/B.
Now, negative electrode active material layer 243A is difficult to peel off from negative electrode collector 241A is comparatively ideal.
Now, as the comparatively ideal negative electrode active material particle 710 for negative electrode active material layer 243A, the present invention's
150 tap densities that inventor proposes negative electrode active material particle 710 are 1g/cm3More than.Figure 12 is to negative electrode active material
Particle 710 represents the relation of 150 tap densities and peel strength.
Here, 150 tap densities are to put into negative electrode active material particle in graduated cylinder, with percussion device mechanically
Percussion graduated cylinder 150 times, makes the apparent volume of negative electrode active material particle reduce.In addition, as shown in figure 13, peel strength be according to
Peel off what adhesive strength test method (JIS K 6854-1) measured for 90 degree.Figure 13 is to represent 90 degree of stripping adhesive strength test sides
The figure of method.
Here, sample 120 is gluing of the negative electrode active material layer 64 laminating day east electrician of the one side in negative plate 66
Connect adhesive tape 105 (No.3303N), and be cut into the size of width 15mm × length 120mm.The sample 120 cutting out from one end start by
Jointing tape 105 peels off only 40mm.Then, in object stage 115 laminating day east electrician's two-sided tape (No.501F).In this pair
On face adhesive tape 110, jointing tape 105 is fitted in said sample 120 down.Then, by the portion of the 40mm of the stripping of sample 120
Divide and be fixed on fixture 125.And, with respect to object stage 115 with 90 ° of stretching clamps 125, measure to peel off from negative electrode collector 62 and bear
The tensile load during active material layer 64 of pole.The stretching of fixture 125 employs Minebea universal testing machine.Draw speed with
20m/min is carried out.Peel strength N/m is that the tensile load (N) obtaining is obtained divided by the width (15mm) of sample 120.
The opinion being obtained according to the present inventor, in the negative electrode active material layer 243A shown in Figure 10, negative pole is lived
Property material particle 710 150 tap densities be general 1g/cm3When above, peel strength uprises.Therefore, form binding agent inclined
During the negative electrode active material layer 243A being distributed near surface A1, it is possible to use 150 tap densities are general 1g/cm3With
Upper, more preferably 1.08g/cm3Above, it is more preferably 1.10g/cm3Above negative electrode active material particle 710.Thus,
Suitable peel strength can be guaranteed in negative electrode active material layer 243A.
As described above, possess negative electrode collector 241A keep negative electrode active material layer 243A negative plate 240A non-aqueous
It is in secondary cell, as shown in Figure 10, the binding agent 730 contained by negative electrode active material layer 243A can comprise elastomeric adhesive
Or there is the resin (for example, acrylic adhesive, imide series binding agent) of binding agent function.Now, elastomeric adhesive
Or the resin with binding agent function is included in the table of negative electrode active material layer 243A in negative electrode active material layer 243A mostly
Face A1 (deflection distribution) nearby.
In addition, utilizing above-mentioned non-aqueous secondary battery, the near surface A1 in negative electrode active material layer 243A, a large amount of bags
Containing elastomeric adhesive or the resin with binding agent function.Using above-mentioned elastomeric adhesive or the tree with binding agent function
Fat, in the secondary battery, can maintain that negative electrode active material layer 243A releases, occlusion becomes the chemistry of charge carrier higher
Plant response speed when (for example, being lithium ion in lithium rechargeable battery).Thus, particularly in -15 DEG C about of low temperature
Under environment, the resistance increment rate after charge and discharge cycles can be suppressed relatively low.
Now, near surface A1 can specify that in negative electrode active material layer 243A from a surface to 1/4 thickness area
Domain.Now, by the elastomeric adhesive contained by the near surface A1 of negative electrode active material layer 243A and there is binding agent function
Resin carry out total mass concentration A with by negative electrode active material layer 243A except the partly contained rubber of near surface A1
Be binding agent and have binding agent function resin carry out total mass concentration B ratio A/B can for 2.0≤(A/B)≤
3.8.Thus, under -15 DEG C about of low temperature environment, the resistance increment rate after charge and discharge cycles more reliably can be suppressed
Lower.Now, above-mentioned can be preferably 2.1≤(A/B) than A/B, can be more preferably 2.2≤(A/B).In addition, it is above-mentioned
(A/B)≤3.7 can be preferably than A/B, (A/B)≤3.6 can be more preferably.Thereby, it is possible to further reliably by charge and discharge
Resistance increment rate after electricity circulation suppresses relatively low.
In addition, contained elastomeric adhesive in binding agent or the resin with binding agent function can be divided
Dissipate the binding agent in aqueous solvent.In addition, now, elastomeric adhesive can be for example SBR.In addition, having binding agent function
Resin in comprise acrylic adhesive.Acrylic adhesive can comprise to be selected from poly(ethylene oxide), in polyethylene
At least one binding agent.
In addition, now, 150 tap densities of negative electrode active material particle can be 1g/cm3More than.Thereby, it is possible to carry
The peel strength of high negative electrode active material layer 243A, by make binding agent 730 be partial to negative electrode active material layer 243A surface attached
Nearly A1 and be distributed, the reduction of the peel strength of negative electrode active material layer 243A can be suppressed less.
In addition, above-mentioned non-aqueous secondary battery may be constructed lithium ion battery.Should illustrate, in addition, the invention is not restricted to
Any of the above described embodiment.For example, in the above-described embodiment, non-aqueous secondary battery is exemplified with lithium rechargeable battery, but
Present invention may apply to beyond lithium rechargeable battery.Non-aqueous secondary battery can combine multiple and constitute set of cells.Separately
Outward, after the non-aqueous secondary battery of the present invention also can be by charge and discharge cycles particularly under -15 DEG C about of low temperature environment
Resistance increment rate suppresses relatively low.Therefore, be particularly well-suited to constitute requirement will be above-mentioned for above-mentioned non-aqueous secondary battery and set of cells
The vehicle traction battery that resistance increase under low temperature environment suppresses relatively low.
This concludes the description of the non-aqueous secondary battery of one embodiment of the present invention, but the secondary electricity of non-water system of the present invention
Pond is not limited to any of the above described embodiment, can carry out various changes.
Non-aqueous secondary battery disclosed herein enables in particular to suppress relatively low by the resistance increment rate under low temperature environment, energy
Enough offers play the non-aqueous secondary batteries such as high performance lithium rechargeable battery at low ambient temperatures.Therefore, according to the present invention
Can provide that to possess above-mentioned non-aqueous secondary battery 10 as shown in figure 14 (can be that this non-aqueous secondary battery 10 multiple are connected
The form of the set of cells connecting and being formed) as power supply (vehicle traction battery) vehicle 1000 (typically automobile, especially
It is the automobile possessing motor of hybrid vehicle, electric automobile etc).
Symbol description
10 vehicle traction batteries
100th, 100A lithium rechargeable battery (non-aqueous secondary battery)
200 rolled electrode bodies
220 positive plates
221 positive electrode collectors
222 uncoated portions
223 positive electrode active material layers
224 mid portions
225 gaps
240th, 240A negative plate
241st, 241A negative electrode collector
242nd, 242A uncoated portion
243rd, 243A negative electrode active material layer
262nd, 264 distance piece
280 electrolyte
290 chargers
300 battery containers
320 container bodies
340 lids
350 liquid injection holes
352 seal caps
360 relief valve
420 electrode terminals
440 electrode terminals
610 positive active material particles
620 conductive materials
630 binding agents
710 negative electrode active material particles
730 binding agents
1000 vehicles
Claims (8)
1. a kind of non-aqueous secondary battery, possesses negative electrode collector and the negative electrode active material being held in described negative electrode collector
Layer,
Described negative electrode active material layer comprises negative electrode active material particle and binding agent,
Described adhesive comprises at least in elastomeric adhesive, acrylic adhesive and imide series binding agent
Kind,
Described negative electrode active material layer has single layer structure, and described single layer structure is described negative by disperseing in water solvent
Pole active material particle and cathode agent obtained from described adhesive be coated with described negative electrode collector and be dried and
Formed,
In described negative electrode active material layer, the region from a surface to 1/4 thickness is near surface and described negative electrode active material layer
The part in addition to described near surface compare, comprise more described adhesives,
Mass concentration A of the described adhesive contained by described near surface with by described negative electrode active material layer except surface is attached
The ratio A/B of mass concentration B of partly contained described adhesive beyond near is 2.0≤(A/B)≤3.8,
Wherein, the amount of described water solvent of described cathode agent and the temperature of described drying by with described reach 2.0 than A/B≤
(A/B)≤3.8 mode is adjusted.
2. non-aqueous secondary battery according to claim 1, wherein, what described adhesive was comprised bonds selected from rubber series
At least one binding agent in agent, acrylic adhesive and imide series binding agent can be scattered in aqueous solvent.
3. non-aqueous secondary battery according to claim 1 and 2, wherein, comprises SBR as described elastomeric adhesive.
4. non-aqueous secondary battery according to claim 1 and 2, wherein, shakes for 150 times of described negative electrode active material particle
Real density is 1g/cm3More than.
5. non-aqueous secondary battery according to claim 1 and 2, wherein, is constituted in the form of lithium ion battery.
6. non-aqueous secondary battery according to claim 1 and 2, wherein, described negative electrode active material layer is according to JIS K
Specified in 6854-1, the peel strength of 90 degree of stripping adhesive strength determination of test method is more than 4N/m.
7. a kind of set of cells, is to combine the non-aqueous secondary battery any one of multiple claim 1～6.
8. a kind of vehicle traction battery, wherein, possess non-aqueous secondary battery any one of claim 1～6 or
Set of cells described in claim 7.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2011/073353 WO2013054398A1 (en) | 2011-10-11 | 2011-10-11 | Nonaqueous secondary battery |
Publications (2)
| Publication Number | Publication Date |
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| CN103875096A CN103875096A (en) | 2014-06-18 |
| CN103875096B true CN103875096B (en) | 2017-02-22 |
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| CN201180074108.XA Active CN103875096B (en) | 2011-10-11 | 2011-10-11 | Nonaqueous secondary battery |
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| US (1) | US10014524B2 (en) |
| JP (1) | JP5924550B2 (en) |
| KR (2) | KR101875254B1 (en) |
| CN (1) | CN103875096B (en) |
| DE (1) | DE112011105726T5 (en) |
| WO (1) | WO2013054398A1 (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6201425B2 (en) * | 2013-05-23 | 2017-09-27 | 日立化成株式会社 | Negative electrode material for lithium ion secondary battery, negative electrode for lithium ion secondary battery, and lithium ion secondary battery |
| JP5991551B2 (en) * | 2014-01-08 | 2016-09-14 | トヨタ自動車株式会社 | Nonaqueous electrolyte secondary battery |
| JP6249242B2 (en) | 2015-04-06 | 2017-12-20 | トヨタ自動車株式会社 | Nonaqueous electrolyte secondary battery |
| JP6264320B2 (en) | 2015-04-14 | 2018-01-24 | トヨタ自動車株式会社 | Nonaqueous electrolyte secondary battery and manufacturing method thereof |
| KR102065733B1 (en) * | 2015-10-21 | 2020-01-13 | 주식회사 엘지화학 | Electrode composite, secondary battery and cable type secondary battery including the same |
| CN109314216B (en) * | 2016-06-08 | 2021-08-17 | 远景Aesc 日本有限公司 | Nonaqueous electrolyte secondary battery |
| EP3471189B1 (en) * | 2016-06-08 | 2020-03-25 | Envision AESC Japan Ltd. | Nonaqueous electrolyte secondary battery |
| JP6585843B2 (en) * | 2016-06-08 | 2019-10-02 | 株式会社エンビジョンＡｅｓｃジャパン | Nonaqueous electrolyte secondary battery |
| WO2018179894A1 (en) * | 2017-03-31 | 2018-10-04 | 株式会社村田製作所 | Lithium-ion secondary battery |
| CN113169295B (en) * | 2018-11-30 | 2024-04-05 | 松下知识产权经营株式会社 | Negative electrode for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery |
| KR20200132749A (en) | 2019-05-15 | 2020-11-25 | 에스케이이노베이션 주식회사 | Lithium secondary battery |
| CN114616708A (en) * | 2019-10-31 | 2022-06-10 | 三洋电机株式会社 | Nonaqueous electrolyte secondary battery |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4761010B1 (en) * | 2010-10-13 | 2011-08-31 | トヨタ自動車株式会社 | Electrode plate, secondary battery, and electrode plate manufacturing method |
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| JP3726163B2 (en) | 1994-10-27 | 2005-12-14 | 宇部興産株式会社 | Non-aqueous secondary battery and manufacturing method thereof |
| JP3482443B2 (en) | 1997-03-27 | 2003-12-22 | 日本電池株式会社 | Electrode for non-aqueous electrolyte secondary battery and method for producing the same |
| JP2007012559A (en) * | 2005-07-04 | 2007-01-18 | Sony Corp | Battery |
| JP2007234418A (en) * | 2006-03-01 | 2007-09-13 | Matsushita Electric Ind Co Ltd | Negative electrode mixture paste for nonaqueous secondary battery, negative electrode and nonaqueous secondary battery using it as well as manufacturing method of negative electrode mixture paste |
| JP5260851B2 (en) | 2006-09-28 | 2013-08-14 | Ｎｅｃエナジーデバイス株式会社 | Lithium ion secondary battery |
| JP5316862B2 (en) * | 2009-02-04 | 2013-10-16 | 株式会社豊田自動織機 | Negative electrode for lithium ion secondary battery and method for producing the same |
| WO2010089898A1 (en) * | 2009-02-09 | 2010-08-12 | トヨタ自動車株式会社 | Lithium secondary battery |
| US8986883B2 (en) * | 2009-11-16 | 2015-03-24 | National University Corporation Gunma University | Negative electrode for lithium secondary battery and method for producing same |
| US20120328942A1 (en) | 2010-03-05 | 2012-12-27 | A123 Systems, Inc. | Design and fabrication of electrodes with gradients |
| DE112011101607T5 (en) | 2010-05-12 | 2013-04-11 | Kabushiki Kaisha Toyota Jidoshokki | Electrode for lithium ion secondary battery and manufacturing method therefor |
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2011
- 2011-10-11 KR KR1020147010691A patent/KR101875254B1/en active IP Right Grant
- 2011-10-11 WO PCT/JP2011/073353 patent/WO2013054398A1/en active Application Filing
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- 2011-10-11 DE DE112011105726.1T patent/DE112011105726T5/en active Pending
- 2011-10-11 CN CN201180074108.XA patent/CN103875096B/en active Active
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| JP4761010B1 (en) * | 2010-10-13 | 2011-08-31 | トヨタ自動車株式会社 | Electrode plate, secondary battery, and electrode plate manufacturing method |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101875254B1 (en) | 2018-07-05 |
| WO2013054398A1 (en) | 2013-04-18 |
| US10014524B2 (en) | 2018-07-03 |
| KR20160084477A (en) | 2016-07-13 |
| US20140272540A1 (en) | 2014-09-18 |
| CN103875096A (en) | 2014-06-18 |
| JPWO2013054398A1 (en) | 2015-03-30 |
| DE112011105726T5 (en) | 2014-07-10 |
| KR20140072116A (en) | 2014-06-12 |
| JP5924550B2 (en) | 2016-05-25 |
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